JPH05271685A - Oil or fat composition containing highly unsaturated fatty acid and production of glyceride oil containing highly unsaturated fatty acid - Google Patents

Abstract

PURPOSE:To provide an oil and fat compsn. which allows effective intake of highly unsatd. fatty acids such as eicosapentaenoic acid and docosahexaenoic acid into the body and provide the method for easily producing a glyceride oil contg. a large amt. of those acids. CONSTITUTION:This oil and fat compsn. contains eicosapentaenoic acid and docosahexaenoic acid each in an amt. of at least 16wt.%, the sum of highly unsatd. fatty acids contained in the compsn. being at least 40wt.%. The objecting glyceride oil is produced by treating an oil or fat contg. highly unsatd. fatty acids with an enzyme and bringing the resulting mixture of a glyceride oil contg. the acids with free fatty acids into contact with a hydrophilic permeable membrane to remove the free acids.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly unsaturated fatty acid, and more particularly to an oil containing a large amount of both eicosapentaenoic acid and docosahexaenoic acid. The present invention also relates to a method for producing a glyceride oil containing highly unsaturated fatty acids such as eicosapentaenoic acid and docosahexaenoic acid.

[0002]

2. Description of the Related Art A wide variety of fatty acids are mixed in fats and oils. Among them, n-3 highly unsaturated fatty acids such as eicosapentaenoic acid and docosahexaenoic acid (n represents the number from the methyl group end of the fatty acid to the carbon having the first double bond) is prostaglandin. In the context of gin, thromboxane and the like, attention has been paid to their physiological activity.

Further, eicosapentaenoic acid is said to be effective for the treatment and prevention of arteriosclerosis, and the docosahexaenoic acid component has hitherto been said to have a brain-healing action, and treatment and prevention of various adult diseases. Therefore, the development of pharmaceuticals and foods is underway. For example, as a drug,
Regarding the use for treating and preventing arteriosclerosis, JP-A-58-58
No. 18374, and a therapeutic agent for peripheral blood flow disorder is described in JP-A-58-180423.
Cholesterol is described in JP-A-55-92316 and JP-A-57-31614.
Further, regarding the use as an anticancer agent composition, JP-A-63-
It is described in Japanese Patent No. 258816. Further, Japanese Patent Application Laid-Open No. 1-49723 describes a therapeutic agent for dementia and improvement of brain function.

In the field of foods, effective utilization of fish oils containing highly unsaturated fatty acids and fats and oils derived from plants, microorganisms, etc. has been studied, and along with that, fats and oils containing necessary components in a concentrated manner and their contents. Processed foods have already been proposed. For example, JP 60-98963 A and JP 6
0-102168 and the like describe foods fortified with eicosapentaenoic acid, and foods containing a high content of highly unsaturated fatty acids are disclosed in JP-A-60-192546,
It is described in JP-A-61-58536.

[0005]

[Problems to be Solved by the Invention] However, in the past,
Polyunsaturated fatty acids in the field of pharmaceuticals are mainly
It is used in the form of fatty acid ester, but it is said that fatty acid ester is inferior to glyceride in absorption (M.Re
icks et al, Lipids, 25 , 6, 1990). On the other hand, as the highly unsaturated fatty acid in the food field, even when it is used in the form of glyceride, one in which only one of eicosapentaenoic acid and docosahexaenoic acid is concentrated is used. 1 unsaturated fatty acid each
The fats and oils containing 6% by weight or more have heretofore been hardly known commercially. So now that the population is aging,
Since the intake amount of oils and fats tends to decrease with age, an oil and fat composition that can be efficiently ingested is desired in the fields of food and medicine.

Therefore, an object of the present invention is to provide an oil and fat composition for efficiently ingesting highly polyunsaturated fatty acids effective in the body such as eicosapentaenoic acid and docosahexaenoic acid. Another object of the present invention is to provide a method for easily producing a glyceride oil containing a large amount of highly unsaturated fatty acids such as eicosapentaenoic acid and docosahexaenoic acid.

[0007]

According to the present invention, 16% by weight of eicosapentaenoic acid and 16% by weight of docosahexaenoic acid are contained.
The above object is achieved by providing a highly unsaturated fatty acid-containing oil or fat composition containing a total of 40% by weight or more of highly unsaturated fatty acids in total. Further, the present invention, by enzymatically treating a fat or oil containing a polyunsaturated fatty acid, a mixture of the obtained glyceride oil containing a polyunsaturated fatty acid and a free fatty acid is brought into contact with a hydrophilic permeable membrane,
Another object of the above is achieved by providing a method for producing a glyceride oil containing a polyunsaturated fatty acid, which is characterized in that the free fatty acid is separated.

That is, in the first invention of the present invention, eicosapentaenoic acid and docosahexaenoic acid each account for 16% by weight.
Further, the present invention provides a highly unsaturated fatty acid-containing oil or fat composition containing a total of 40% by weight or more of highly unsaturated fatty acids. The highly unsaturated fatty acid-containing oil / fat composition of the present invention contains eicosapentaenoic acid and docosahexaenoic acid in an amount of 16% by weight or more, usually 16 to 40% by weight, preferably 20 to 30% by weight, and further, a highly unsaturated fatty acid. Is 40% by weight or more, usually 40 to 80% by weight,
Preferably, it contains 50 to 65% by weight.

The polyunsaturated fatty acid-containing oil and fat composition of the present invention contains eicosapentaenoic acid and docosahexaenoic acid in an amount of 16% by weight or more, and eicosapentaenoic acid, docosahexaenoic acid, and other highly unsaturated fatty acids in a total of 40% by weight or more. If so, the composition and origin are not limited. The highly unsaturated fatty acid referred to in the present invention is a fatty acid having 18 or more carbon atoms, particularly 18 to 22 carbon atoms, and having 3 or more double bonds. Specifically, linolenic acid (having 18 carbon atoms
・ Double bond 3), octadecatetraenoic acid (C18
・ Double bond 4), icosatrienoic acid (20 carbon atoms, double bond 3), icosatetraenoic acid (20 carbon atoms, double bond 4), eicosa (new name is icosa) pentaenoic acid (20 carbon atoms, 2 carbon atoms) Heavy bond 5), icosahexaenoic acid (carbon number 20 / double bond 6), docosatrienoic acid (carbon number 22 /
Double bond 3), docosatetraenoic acid (22 carbons / double bond 4), docosapentaenoic acid (22 carbons / double bond 5), docosahexaenoic acid carbon number (22 carbons / double bond 6) Etc.

The polyunsaturated fatty acid-containing oil / fat composition of the present invention may be added with an antioxidant in consideration of oxidative deterioration of the oil / fat, or may be microencapsulated or powdered with a peptide or the like. It may be processed and used. further,
The highly unsaturated fatty acid-containing oil / fat composition of the present invention may be optionally blended with an oil / fat containing a highly unsaturated fatty acid such as eicosapentaenoic acid and docosahexaenoic acid.

Furthermore, the highly unsaturated fatty acid-containing oil or fat composition of the present invention may be added to ordinary processed foods. For example, breads and noodles as starch foods, kamaboko as water-mixed meat products, sausages, milk as milk products, yogurt, pudding, ice cream, powdered milk, chocolate as confectionery, cookies, fats and oils products. , Shortening, margarine, dressing, mayonnaise, etc., as well as miso, prepared foods, retort foods, various drinks called healthy drinks, liquid foods for medical use, etc.

Next, the method for producing a glyceride oil containing a polyunsaturated fatty acid, which is the second invention of the present invention, will be explained. The second invention of the present invention is obtained by enzymatically treating a fat or oil containing a polyunsaturated fatty acid, a mixture of a glyceride oil containing a polyunsaturated fatty acid and a free fatty acid is contacted with a hydrophilic permeable membrane, A method for producing a glyceride oil containing a polyunsaturated fatty acid, which separates the free fatty acid is provided.

That is, the raw fats and oils are hydrolyzed with an enzyme to concentrate highly unsaturated fatty acids on the glyceride oil side of the raw fats and oils. Then, the concentrated raw material fat is in a state of mixing the glyceride oil containing the polyunsaturated fatty acid and the free fatty acid, so that the mixture is brought into contact with the hydrophilic permeable membrane to separate the free fatty acid. A glyceride oil containing highly unsaturated fatty acids is produced.

The main raw material fats and oils that provide highly unsaturated fatty acids are fish oil, whale oil, liver oil, fats and oils obtained from shellfish,
Examples include oil under fish eyes, oils and fats obtained from algae, oils and fats produced by microorganisms, and the like. The raw material fats and oils are general edible fats and oils, for example, soybean oil, rapeseed oil, cottonseed oil, corn oil, olive oil, rice oil, palm oil, safflower oil, sunflower oil, cocoa butter, lard and the like mixed fats and oils. Can also be used.

Further, it is also possible to use an oil or fat obtained by fractionating the above-mentioned raw material oil or mixed oil or fat, or a transesterified oil of the above raw material oil or mixed oil or fat. The transesterified oil is obtained by transesterifying a fat and oil or a fat or a fat and a highly unsaturated fatty acid such as eicosapentaenoic acid and docosahexaenoic acid or a highly unsaturated fatty acid lower alcohol ester with an enzyme, an alkali or an acid by a conventional method. Be done.

The content of eicosapentaenoic acid and docosahexaenoic acid in the raw material fat used in the present invention,
Further, the content of the entire polyunsaturated fatty acid is not limited at all, but the content of eicosapentaenoic acid and docosahexaenoic acid is 5% by weight or more, preferably 8% by weight or more, and the highly unsaturated fatty acid is The total content is 2
It is preferable to use 0 wt% or more, preferably 25 wt% or more. This is effective in simplifying the concentration process and reducing losses during the process.

The concentration of the raw material oil and fat in the second aspect of the present invention is carried out by enzymatic treatment, that is, hydrolysis. The enzyme to be used may be any lipase having a fatty acid selectivity such that it is difficult to act on the bond between highly unsaturated fatty acid and glycerin, that is, hydrolysis is unlikely to occur, and the genus Candida, Geotricum (Geotricum) can be used.
) Lipases derived from genus and the like. The genus Candida includes Candida cylindracea and Geotricam.
As a genus of cum, Geotricum candydium (G
eotricum candidum) and the like, and lipase derived from Candida cylindracea is preferable.

The enzyme is used in an amount of 10 to 100 relative to the raw material oil and fat.
0 U (unit), preferably 50 to 500 U may be added. The enzyme treatment is carried out at a temperature of 30 to 60 ° C.
It is carried out until the decomposition rate becomes 20 to 80%, preferably 30 to 70%. The above treatment gives a mixture of glyceride oil containing polyunsaturated fatty acids and free fatty acids.

Next, as a method for separating the free fatty acid from the mixture of the glyceride oil containing the polyunsaturated fatty acid and the free fatty acid obtained by the enzyme treatment, the mixture is brought into contact with a hydrophilic permeable membrane. Do it. Examples of the hydrophilic permeable membrane to be used include microfiltration membranes and ultrafiltration membranes obtained by a wet method composed of polyimide, polyamide, cellulose acetate, ethylene-vinyl alcohol copolymer and the like. The shape is not limited to a flat plate shape, a tubular shape, a hollow fiber shape, and the like.

Further, an ultrafiltration membrane in which the molecular weight cut-off of the dense layer of the hydrophilic permeable membrane is in the range of 1,000 to 1,000,000 and the fine pore diameter of the porous material is in the range of 0.1 to 100 μm is preferable. .. Furthermore, in the present invention, it is preferable to combine the membrane separation method in which the hydrophilic permeable membrane is brought into contact with the membrane for liquid-liquid extraction method.

That is, an organic solvent that dissolves the free fatty acid is added to a mixture of a glyceride oil containing a polyunsaturated fatty acid and the free fatty acid, and the mixture is stirred to form an O / W type emulsion. The free fatty acid permeates the membrane together with the organic solvent by contact with the membrane. On the other hand, a glyceride oil containing a polyunsaturated fatty acid does not permeate through the membrane and can be obtained as a membrane concentrate, and the free fatty acid can be efficiently obtained from a mixture of a glyceride oil containing a polyunsaturated fatty acid and a free fatty acid. Can be separated.

In the O / W type emulsion of the present invention, the O component essentially consists of glyceride oil, and the W component consists of organic solvent and free fatty acid. As the organic solvent, hydrophilic organic solvents such as methanol, ethanol, propanol and butanol are used. These organic solvents may contain a small amount of water, or may be a mixture of two or more kinds.

The amount of the organic solvent added is not particularly limited as long as it forms an O / W emulsion, but the weight ratio of the concentrated raw material fat and oil to the organic solvent is 1: 1.
It is preferable to add them in a ratio of 1 to 10. Membrane separation is preferably performed under pressure. The pressurization is not particularly limited as long as the emulsion particles, that is, the glyceride oil does not permeate the membrane, but is usually 0.1
~ 3 Kg / cm ² is preferred.

The membrane separation may be carried out usually at 10 to 60 ° C, preferably at 20 to 40 ° C. The recovery of the highly unsaturated fatty acid by the above method is very efficient, and the recovery rate is 50% or more, preferably 60% or more based on the raw material fat. Finally, the highly unsaturated fatty acid-containing oil / fat composition of the first invention of the present invention can be easily produced by the method for producing a glyceride oil containing a highly unsaturated fatty acid of the second invention. However, the manufacturing method is not limited thereto.

That is, in the concentration step for obtaining the highly unsaturated fatty acid-containing fat of the first invention, the respective contents of eicosapentaenoic acid and docosahexaenoic acid are economically and industrially 16% by weight or more. And, and
As long as the total amount of highly unsaturated fatty acids is economically and industrially 40% by weight or more, the concentrate obtained by the above enzyme treatment may be mixed with the concentrate obtained by another method. is there.

Examples of other concentrating methods include wintering, solvent fractionation with acetone or hexane, chromatographic separation, esterification, transesterification and the like. Generally, wintering, acetone or Solvent fractionation such as hexane is used. Further, in the step of separating the free fatty acid when obtaining the highly unsaturated fatty acid-containing oil or fat of the first invention, in addition to the above-mentioned membrane separation method, a commonly used alkali deoxidation method, silica gel, florisil, etc. are filled. The method using adsorption by the column chromatography, the method by liquid-liquid extraction, the method by distillation by utilizing the boiling point difference under vacuum, and the like may be combined.

Further, the method for producing a glyceride oil containing a polyunsaturated fatty acid of the second invention is not limited to the polyunsaturated fatty acid-containing oil and fat of the first invention, and the respective contents of eicosapentaenoic acid and docosahexaenoic acid, and Of course, it is possible to produce even fats and oils whose total content of polyunsaturated fatty acids is lower than that of the polyunsaturated fatty acid-containing fats and oils of the first invention.

[0028]

INDUSTRIAL APPLICABILITY The highly unsaturated fatty acid-containing oil / fat composition of the present invention can be ingested efficiently because the highly unsaturated fatty acid having useful physiological activity in the body is concentrated in the form of glyceride oil. Further, the highly unsaturated fatty acid-containing oil and fat composition of the present invention, by adding to various foods, it is possible to ingest a constant amount of eicosapentaenoic acid and docosahexaenoic acid in a form close to nature, various adult diseases Effective for prevention and improvement.

Furthermore, by the method for producing a highly unsaturated fatty acid-containing oil / fat composition of the present invention, an oil / fat containing a large amount of highly unsaturated fatty acid can be easily produced.

[0030]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0031]

Example 1 To 200 g of refined fish oil (derived from sardines, 15% by weight of eicosapentaenoic acid, 10% by weight of docosahexaenoic acid, and 33% by weight of highly unsaturated fatty acids), 250 U of lipase (from Candida) was used per 1 g of oil. Three
After hydrolysis at 7 ° C. for 3 hours, 186 g of hydrolyzed fish oil (weight ratio of triglyceride / diglyceride / monoglyceride / free fatty acid 39/8/2/51) was obtained.

To this hydrolyzed fish oil, 300 ml of 75% (V / V) ethanol was added to prepare an O / W type emulsion. The above emulsion was placed in a membrane separation tank equipped with a flat polyimide ultrafiltration membrane having a molecular weight cut-off of 20,000 and stirred at room temperature and pressurized with 1 to 1.5 kg / cm ² of nitrogen, and 75% from a reservoir. While replenishing with 3200 ml of (V / V)% ethanol, 3250 ml of the membrane permeate was separated to obtain a membrane concentrate. The membrane concentrate was distilled to remove the solvent to obtain about 92 g of glyceride oil.

The obtained glyceride oil was 21% by weight of eicosapentaenoic acid, 21% by weight of docosahexaenoic acid, and 52% by weight of total polyunsaturated fatty acid, and the amount of free fatty acid was 1.6% by weight. The recovery rate of highly unsaturated fatty acids from the raw fish oil was 72%. The above glyceride oil is bleached and deodorized by a conventional method to obtain a highly unsaturated fatty acid-containing deodorized oil A (21% by weight of eicosapentaenoic acid of the present invention,
21% by weight of docosahexaenoic acid and a total of 52% by weight of highly unsaturated fatty acids) were obtained.

[0034]

Example 2 300 g of the same refined fish oil as in Example 1 was -30
Fractionated and purified fish oil (23% by weight of eicosapentaenoic acid) obtained by fractionating the acetone at ℃ and removing the solvent from the soluble fraction.
117 g of docosahexaenoic acid and 44% by weight of polyunsaturated fatty acid) was added to 400 g of lipase (from Candida) per 1 g of oil, and hydrolyzed for 40 minutes at 37 ° C. to give hydrolyzed fish oil (triglyceride / diglyceride). And monoglyceride / free fatty acid weight ratio 55/14 /
31) 117 g were obtained.

117 g of the obtained hydrolyzed fish oil was injected into a column packed with 500 g of Florisil PR (Wako Pure Chemical Industries, Ltd.) in an amount of 10 g each, and 5 l of ether / methanol (98/2) was added as an eluent. The solution was passed to obtain a glyceride oil fraction, and the solvent was removed by distillation to obtain a total of about 81 g of glyceride oil. When the fatty acid composition of this glyceride oil was measured, it was found to be 26% by weight of eicosapentaenoic acid, 19% by weight of docosahexaenosan, and 55% by weight of highly unsaturated fatty acid in total. The recovery rate of highly unsaturated fatty acids from the raw fish oil was 45%.

The glyceride oil was bleached and deodorized by a conventional method to obtain a highly unsaturated fatty acid-containing deodorized oil B (26% by weight of eicosapentaenoic acid, 19% by weight of docosahexaenoic acid, total 55% by weight of highly unsaturated fatty acid). ..

[0037]

Example 3 500 g of purified fish oil (derived from sardines, 14% by weight of eicosapentaenoic acid, 10% by weight of docosahexaenoic acid, 32% by weight of all highly unsaturated fatty acids) was subjected to solvent fractionation at -40 ° C with acetone to obtain 85 g of a liquid oil. Obtained. The composition of the obtained liquid oil was 26% by weight of eicosapentaenoic acid, 13% by weight of docosahexaenoic acid, and 49% by weight of highly unsaturated fatty acid in total. The recovery rate of highly unsaturated fatty acids from the raw fish oil was 26%.

The liquid oil was desolvated by a conventional method, bleached and deodorized to obtain a highly unsaturated fatty acid-containing deodorized oil c (the composition is as described above). The highly unsaturated fatty acid-containing deodorized oil B obtained in Example 2 and the highly unsaturated fatty acid-containing deodorized oil c described above were mixed in a ratio of 6: 4 (parts by weight) to prepare a highly unsaturated fatty acid-containing deodorized oil C of the present invention. (26% by weight of eicosapentaenoic acid, 17% by weight of docosahexaenoic acid, total of 5 highly unsaturated fatty acids)
2% by weight).

[0039]

Example 4 To 30 g of each of the highly unsaturated fatty acid-containing deodorized oils A to C obtained in Examples 1 to 3, 10 g of egg white hydrolyzate (a peptide hydrolyzed with a protease to an average molecular weight of about 1100), casein 10 g of sodium, 0.05 g of vitamin E and 500 ml of water were added, and the mixture was uniformly emulsified with a high-pressure homogenizer and then spray-dried to obtain powdered oil A to
50 g of each C was obtained.

[0040]

[Example 5] Powder oils and fats A to C obtained in Example 4 (5 g each)
Was added to 100 g of miso to obtain 105 g of highly unsaturated fatty acid-enriched miso A to C.

[0041]

Example 6 10 ml of rice vinegar was added to 10 ml of each of the highly unsaturated fatty acid-containing deodorized oils A to C obtained in Examples 1 to 3, and vitamin E 0.05 g, salt, pepper, garlic, ginger rosemary, etc. An appropriate amount of spices and powdered broth were added and stirred to obtain 20 ml of highly unsaturated fatty acid-enriched dressings A to C by a conventional method.

[0042]

Example 7 Using the highly unsaturated fatty acid-containing deodorized oils A to C obtained in Examples 1 to 3, ice creams were prepared as follows. Loosen 3 egg yolks and 3 milk
After adding 0 ml and spreading, 100 g of sugar, 10 g of corn starch and an appropriate amount of salt were added to and mixed with this.

Separately, 15 g of the above oils and fats was added to 300 ml of milk, and the mixture was uniformly emulsified with a homogenizer, heated to 37 ° C., filtered through a mesh, and then added to the above yolk mixture. The obtained mixture was heated and stirred until it thickened, and then a small amount of essence and brandy was added while cooling the container with ice water. Add 150 ml of fresh cream which is whipped for about 5 minutes, stir and pour into a mold at -15 ° C.
Then, cool and solidify for 1-2 hours with ice cream A-C66
5 g was obtained.

[0044]

Example 8 Powdered fats A to C obtained in Example 4 were added at a ratio of 3 g to 100 g of wheat flour to prepare bread dough, which was baked at 60 ° C. for 30 minutes to obtain breads A to C. It was

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masami Koike 7-35, Higashiohisa, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. (72) Inventor Yuko Sahashi 1-2-1, Shimohozumi, Ibaraki-shi, Osaka Issue Nitto Denko Corporation (72) Inventor Hirotoshi Ishizuka 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation

Claims (2)

[Claims] 1. A highly unsaturated fatty acid-containing oil or fat composition comprising eicosapentaenoic acid and docosahexaenoic acid in an amount of 16% by weight or more and a polyunsaturated fatty acid content of 40% by weight or more in total. 2. A fat or oil containing a polyunsaturated fatty acid is enzymatically treated, and the obtained mixture of a glyceride oil containing a polyunsaturated fatty acid and a free fatty acid is brought into contact with a hydrophilic permeable membrane to release the mixture. A method for producing a glyceride oil containing a polyunsaturated fatty acid, which comprises separating a fatty acid.